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Electronic Supplemental Information (ESI)

DOI

Turn on of Sky-Blue Thermally Activated Delayed Fluorescence and Circularly Polarized Luminescence (CPL) via Increased Torsion by a Bulky

Carbazolophane Donor

Nidhi Sharma,†a,b Eduard Spuling,†c Cornelia M. Mattern,c Wenbo Li,b Olaf Fuhr,d Youichi Tsuchiya,e,f Chihaya Adachi,e,f,g,h Stefan Bräse,*c,d Ifor D. W. Samuel,*b and Eli Zysman-Colman*a

a. Organic Semiconductor Centre, EaStCHEM School of Chemistry, University of St Andrews, St Andrews, Fife, KY16 9ST, UK E-mail: eli.zysman-colman@st-andrews.ac.uk

b. Organic Semiconductor Centre, SUPA, School of Physics and Astronomy, University of St Andrews, North Haugh, St Andrews, KY16 9SS, UK E-mail: idws@st-andrews.ac.uk.

c. Institute of Organic Chemistry (IOC), Karlsruhe Institute of Technology (KIT), Fritz-Haber-Weg 6, 76131 Karlsruhe, Germany E-mail: braese@kit.edu.

d. Institute of Toxicology and Genetics (ITG), Karlsruhe Institute of Technology (KIT), Hermann-von-Helmholtz-Platz 1, D-76344 Eggenstein-Leopoldshafen, Germany

e. Center for Organic Photonics and Electronics Research (OPERA), Kyushu University, 744 Motooka, Nishi-ku, Fukuoka 819-0395, Japan.

f. JST, ERATO, Adachi Molecular Exciton Engineering Project, Kyushu University, 744 Motooka, Nishi-ku, Fukuoka 819-0395, Japan.

g. Department of Chemistry and Biochemistry, Kyushu University, 744 Motooka, Nishi-ku, Fukuoka 819-0395, Japan.

h. International Institute for Carbon Neutral Energy Research (WPI-I2CNER), Kyushu University, 744 Motooka, Nishi-ku, Fukuoka 819-0395, Japan.

† Nidhi Sharma and Eduard Spuling contributed equally to this work. Electronic Supplementary Information (ESI) available: [details of any supplementary information available should be included here]. See DOI: 10.1039/x0xx00000x

Electronic Supplementary Material (ESI) for Chemical Science.This journal is © The Royal Society of Chemistry 2019

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Table of Contents

1. Prior Literature examples on CPL active TADF materials ............................................................... 2

2. General Experimental Information .................................................................................................. 3

3. Nomenclature of [2.2]Paracyclophanes ........................................................................................... 5

4. Synthesis of Compounds ................................................................................................................. 6

5. Chiral Separation and Determination of Alsolute Configuration .................................................... 18

6. Crystallography ............................................................................................................................ 20

7. Electrochemical Characterization. ................................................................................................. 21

8. Thermal Analysis. ......................................................................................................................... 21

9. Photophysical Characterization. .................................................................................................... 22

10. DFT modelling ............................................................................................................................. 25

11. Device Characterization. ............................................................................................................... 29

12. References .................................................................................................................................... 30

1. Prior Literature examples on CPL active TADF materials

Figure S1. Prior literature examples of CPL active TADF materials.

DPHN

gLum 1.0 × 10-3 ; gEL N/AEQE N/A

R-1

gLum 1.3 × 10-3 ; gEL N/AEQE 9.1%

CAI-Cz

gLum 1.1 × 10-3 ; gEL 2 × 10-3

EQE 19.8%

BN-CF

gLum 1.2 × 10-3 ; gEL 2 × 10-2

EQE 9.3%

g-BNMe2-Cp

gLum 4.2 × 10-3 ; gEL N/AEQE N/A

Chem. Commun., 2015, 51, 13268

J. Am. Chem. Soc., 2016, 138, 3990

Angew. Chemie. Int. Ed., 2018, 57, 2889

Adv. Funct. Mater., 2018, 28, 1800051

Org. Lett.,2018, 20, 6868

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2. General Experimental Information The NMR spectra of compounds described herein were recorded by a Bruker Avance 300 NMR instrument at

300 MHz for 1H NMR and 75 MHz for 13C NMR, a Bruker Avance 400 NMR instrument at 400 MHz for 1H

NMR and 101 MHz for 13C NMR or a Bruker Avance 500 NMR instrument at 500 MHz for 1H NMR,

125 MHz for 13C NMR and 470 MHz for 19F NMR.

The NMR spectra were recorded at room temperature in deuterated solvents commercially acquired from

Eurisotop. The chemical shift δ is displayed in parts per million [ppm] and the references used were the 1H

and 13C peaks of the solvents themselves: d1-chloroform (CDCl3): 7.26 ppm for 1H and 77.0 ppm for 13C), d6-

dimethyl sulfoxide (DMSO-d6): 2.50 ppm for 1H and 39.4 ppm for 13C.

Evaluation of the signals was done according to first order spectra. For the characterization of centrosymmetric

signals, the signal’s median point was chosen, for multiplets the signal range. The following abbreviations

were used to describe couplings: d = doublet, t = triplet, m = multiplet, dd = doublet of doublet, ddd = doublet

of doublet of doublet, dt = doublet of triplet. Coupling constants “J” are given in Hertz [Hz] in absolute value

with the largest value first. Couplings are given with their respective number of bindings and binding partners,

as far as they could be determined, written as index of the coupling constants. Signals of the 13C spectrum

were assigned with the help of distortionless enhancement by polarization transfer spectra DEPT90 and

DEPT135 and were specified in the following way: DEPT: + = primary or tertiary carbon atoms (positive

DEPT signal), – = secondary carbon atoms (negative DEPT signal), Cquat = quaternary carbon atoms (no DEPT

signal).

The infrared spectra were recorded with an instrument made by Bruker, model IFS 88. Solids were measured

by attenuated total reflection (ATR method). Absorption is given in wave numbers ῡ [cm-1] and was measured

in the range from 3600 cm-1 to 500 cm-1. Characterization of the absorption bands was done in sequence of

transmission strength T with following abbreviations: vs (very strong, 0−9% T), s (strong, 10−39% T), m

(medium, 40−69% T), w (weak, 70−89% T), vw (very weak, 90−100% T) and br (broad).

The electron ionization (EI) and fast atom bombardment (FAB) methods were conducted using an instrument

by Finnigan, model MAT 90 (70 eV), was used with 3-nitrobenzyl alcohol (3-NBA) as matrix and reference

for high resolution. For the interpretation of the spectra, molecular peaks [M]+, peaks of pseudo molecules

[M+H]+ and characteristic fragment peaks are indicated with their mass to charge ratio (m/z) and in case of EI

their intensity in percent, relative to the base peak (100%) is given. In the case of high resolution

measurements, the tolerated error is 0.0005 m/z.

APCI and ESI methods were recorded on a Q Exactive (Orbitrap) mass spectrometer (Thermo Fisher

Scientific, San Jose, CA, USA) equipped with a HESI II probe to record high resolution. The tolerated error

is 5 ppm of the molecular mass. Again, the spectra were interpreted by molecular peaks [M]+, peaks of pseudo

molecules [M+H]+ and characteristic fragment peaks and indicated with their mass to charge ratio (m/z).

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For the analytical thin layer chromatography, TLC silica plates coated with fluorescence indicator, made by

Merck (Art. Nr. 105554, silica gel 60 F254, thickness 0.2 mm) were used. UV active compounds were detected

with a Heraeus UV-lamp, model Fluotest, at 254 nm and 366 nm wavelength.

Solvents of p.a. quality (per analysis) were commercially acquired from Sigma Aldrich, Carl Roth or Acros

Fisher Scientific and, unless otherwise stated, used without previous purification. Absolutized solvents were

either purchased from Carl Roth, Acros or Sigma Aldrich (< 50 ppm H2O over molecular sieve).

All reagents were commercially acquired (through ABCR, Acros, Alfa Aesar or Sigma Aldrich) or were

available in the working group. Unless otherwise stated, they were used without further purification. Elemental

analysis was done with an Elementar vario MICRO instrument. The weight scale used was a Sartorius M2P.

Calculated (calc.) and found values for carbon, hydrogen and nitrogen are indicated in fractions of 100% mass.

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3. Nomenclature of [2.2]Paracyclophanes The IUPAC nomenclature for cyclophanes in general is rather confusing. Therefore Vögtle et al. developed a

specific cyclophane nomenclature, which is based on a core-substituent ranking.[1] This is exemplified in

Figure S2 for the [2.2]paracyclophane.

Figure S2. Nomenclature illustrated on the enantiomers of 4-formyl[2.2]paracyclophane.

The core structure is named according to the length of the aliphatic bridges in squared brackets (e.g. [n.m])

and the benzene substitution patterns (ortho, meta or para). [2.2]Paracyclophane belongs to the D2h symmetry,

which is broken by the first substituent, resulting in two planar chiral enantiomers. They cannot be drawn in

a racemic fashion. By definition, the arene bearing the substituent is set to a chirality plane, and the first atom

of the cyclophane structure outside the plane and closest to the chirality center is defined as the “pilot atom”.

If both arenes are substituted, the substituent with higher priority according to the Cahn-Ingold-Prelog (CIP)

nomenclature is preferred.[2] The stereo descriptor is determined by the sense of rotation viewed from the pilot

atom. To describe the positions of the substituents correctly, an unambiguous numeration is needed. The

numbering of the arenes follows the sense of rotation determined by CIP. To indicate the stereochemistry of

the planar chirality, a subscripted p is added.

In this work, chiral heterocycle-fused derivatives are presented. In this case the cyclophane, and the carbazole

nomenclatures are exerted simultaneously (Figure S3).

Figure S3. Nomenclature of the [2]paracyclo[2](1,4)carbazolophane (short: carbazolophane, Czp).

The first report of the [2]paracyclo[2](1,4)carbazolophane (Czp) by Bolm et al.[3] presented the nomenclature,

but no information on chirality was given The stereo descriptors follow the same standard as reported for the

[2.2]paracyclophane. If viewed as a disubstituted [2.2]paracyclophane, then the nitrogen is assigned a higher

priority than the carbon substituent, resulting in the respective sense of numbering as depicted in red.

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4. Synthesis of Compounds

Scheme S1. Synthetic overview. Synthesis of the carbazolophane published by Bolm et al.[4]

Air-sensitive and moisture-sensitive reactions were carried out under argon atmosphere in previously baked

out apparatuses with standard Schlenk techniques. Solid compounds were ground using a mortar and pestle

before the reaction, liquid reagents and solvents were injected with plastic syringes and stainless-steel cannula

of different sizes, unless otherwise specified.

Reactions at low temperatures were cooled using shallow vacuum flasks produced by Isotherm, Karlsruhe,

filled with a water/ice mixture for 0 °C, water/ice/sodium chloride for –20 °C or isopropanol/dry ice mixture

for –78 °C. In reactions at high temperatures, the reaction flask was equipped with a reflux condenser and

connected to the argon line.

Solvents were evaporated under reduced pressure at the lowest possible temperature (40 °C) using a rotary

evaporator. Unless otherwise stated, solutions of inorganic salts are saturated aqueous solutions.

The progression of the reaction in the liquid phase was monitored via TLC. UV active compounds were

detected with a UV-lamp at 254 nm and 366 nm wavelength. Depending on the confronted problem, the

detection was carried out with vanillin solution, potassium permanganate solution or bromocresol green-

methanol solution followed by heating using a heat gun. Additionally, low resolution APCI-MS (atmospheric

pressure chemical ionization mass spectrometry) was recorded with a device from Advion expression CMS

in positive mode with a single quadrupole mass analyzer. The observed molecule ion is interpreted as [M+H]+.

Unless otherwise stated, the crude compounds were purified by flash chromatography. For the stationary phase

of the column, silica gel, produced by Merck (silica gel 60, 0.040 × 0.063 mm, 260 – 400 mesh ASTM), and

sea sand by Riedel de Haën (baked out and washed with hydrochloric acid) were used. Solvents used were

commercially acquired in HPLC-grade and individually measured volumetrically before mixing.

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rac-4-Bromo[2.2]paracyclophane

To 80.4 mg of iron filings (1.44 mmol, 2 mol%) provided in a 500 mL three neck flask equipped

with a reflux condenser, 5 mL of a solution consisting of 3.77 mL of bromine (11.8 g,

73.7 mmol, 1.02 equiv.) in 80 mL of dichloromethane prepared in a dropping funnel were added

and stirred for 1 h at room temperature. Afterwards, 15.0 g of [2.2]paracyclophane (72.0 mmol,

1.00 equiv.) and 250 mL dichloromethane were added, and the mixture was stirred for 30 min. The remaining

bromine solution was then added dropwise over a period of 4 h and the mixture was stirred for 2 d. The

reaction was quenched with 200mL of saturated sodium sulfite solution and stirred for another 1.5 h until full

discoloration of the reaction mixture. Then, the separated organic phase was washed with 200 mL of brine

and dried over Na2SO4. The solvent was evaporated under reduced pressure to yield 18.2 g (88%, 63.4 mmol)

of a white solid. – Rf = 0.63 (cyclohexane:ethyl acetate 50:1) – 1H NMR (400 MHz, CDCl3) δ [ppm] = 7.19

(dd, 3JHH = 7.9 Hz, 4JHH = 2.0 Hz, 1H), 6.58 (dd, 3JHH = 7.8 Hz, 4JHH = 2.0 Hz, 1H), 6.56 – 6.52 (m, 2H), 6.52

– 6.45 (m, 3H), 3.48 (ddd, 3JHH = 13.0 Hz, 3JHH = 10.1 Hz, 4JHH = 2.2 Hz, 1H), 3.22 (ddd, 3JHH = 13.1 Hz, 3JHH

= 10.1 Hz, 4JHH = 6.1 Hz, 1H), 3.17 – 3.02 (m, 4H), 2.98 – 2.78 (m, 2H). – 13C NMR (101 MHz, CDCl3)

δ [ppm] = 141.73 (Cquat, CAr), 139.43 (Cquat, CAr), 139.22 (Cquat, CAr), 137.37 (+, CArH), 135.17 (+, CArH),

133.43 (+, CArH), 133.03 (+, CArH), 132.37 (+, CArH), 131.59 (+, CArH), 128.81 (+, CArH), 127.09 (Cquat, CAr),

35.98 (–, CH2), 35.61 (–, CH2), 34.95 (–, CH2), 33.61 (–, CH2). – IR (ATR) ṽ [cm–1] = 2924 (w), 2849 (w),

1585 (w), 1541 (w), 1497 (w), 1475 (w), 1431 (w), 1408 (w), 1390 (w), 1186 (w), 1092 (vw), 1034 (m), 941

(w), 869 (w), 839 (m), 793 (w), 708 (m), 668 (w), 640 (m), 576 (w), 514 (m), 473 (w), 404 (vw), 382 (w). –

MS (EI, 70 eV) m/z [%] = 288 (27) [M(81Br)]+, 286 (28) [M(79Br)]+, 184 (17) [C8H781Br]+, 182 (17)

[C8H779Br], 104 (100) [C8H8]+. – HRMS (C16H1579Br) calc. 286.0352; found 286.0350. Analytical data

matches that of the literature.[5]

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rac-4-N-(Phenyl)amino[2.2]paracyclophane

Three pressure vials were each charged with 1.15 g of rac-4-bromo[2.2]paracyclophane

(4.00 mmol, 1.00 equiv.), 62.8 mg potassium tert-butoxide (5.60 mmol, 1.40 equiv.),

10.0 mg SPhos (24.0 µmol, 6 mol%) and 70.0 mg Pd2dba3 (80.0 µmol, 2 mol%) and

evacuated and refilled with argon three times. Then 20 mL of dry toluene and 0.438 mL of

aniline (628 mg, 5.60 mmol, 1.40 equiv.) were added and the mixture was stirred in argon atmosphere at

115 °C for 16 h. The dark brown crude was diluted with 50 mL of water and extracted with 50 mL of ethyl

acetate. Afterwards, the organic layer was washed three times with 50 mL of saturated NH4Cl solution and

with 50 mL of brine. The organic layers were dried over Na2SO4 and the filtrate was evaporated under reduced

pressure. The residue was purified by flash chromatography (silica, 50:1 cyclohexane:ethyl acetate) to yield

3.03 g (84%, 10.1 mmol) of a white solid. – Rf = 0.35 (cyclohexane:ethyl acetate 50:1) – 1H NMR (500 MHz,

CDCl3) δ [ppm] = 7.23 (t, 3JHH = 7.9 Hz, 2H), 7.01 (dd, 3JHH = 7.8, 4JHH = 1.9 Hz, 1H), 6.93 (d, 3JHH = 8.5 Hz,

2H), 6.87 (t, 3JHH = 7.3 Hz, 1H), 6.59 (dd, 3JHH = 7.8, 4JHH = 1.9 Hz, 1H), 6.51 – 6.41 (m, 3H), 6.37 (dd, 3JHH

= 7.8, 4JHH = 1.8 Hz, 1H), 5.86 (d, 3JHH = 1.8 Hz, 1H), 5.55 (bs, 1H), 3.12 – 2.86 (m, 7H), 2.69 (ddd, 3JHH =

13.7, 10.1, 2JHH = 6.8 Hz, 1H). – 13C NMR (126 MHz, CDCl3) δ [ppm] = 143.74 (Cquat, CAr), 141.35 (Cquat,

CAr), 140.21 (Cquat, CAr), 139.64 (Cquat, CAr), 139.13 (Cquat, CAr), 135.99 (+, CArH), 133.64 (+, CArH), 132.85

(+, CArH), 131.48 (Cquat, CAr), 131.34 (+, CArH), 129.28 (+, CArH), 127.55 (+, CArH), 127.04 (+, CArH), 125.99

(+, CArH), 120.17 (+, CArH), 116.09 (+, CArH), 35.35 (–, CH2), 35.01 (–, CH2), 33.95 (–, CH2), 33.93 (–, CH2).

– IR (ATR) ṽ [cm–1] = 3372 (w, v(NH)), 3005 (vw), 2922 (0.85), 2851 (vw), 1591 (w), 1563 (w), 1492 (m),

1433 (w), 1305 (w), 1280 (w), 1239 (w), 1173 (w), 1151 (w), 1108 (w), 1091 (w), 1027 (vw), 996 (vw), 977

(vw), 938 (vw), 886 (w), 800 (w), 780 (vw), 741 (m), 716 (w), 693 (m), 659 (w), 642 (w), 615 (vw), 588 (vw).

). – MS (EI, 70 eV) m/z [%] = 300 (17) [M+H]+, 299 (73) [M]+, 298 (34) [M–H]+, 195 (78) [M–C8H8]+, 194

(84) [M–C8H9]+, 193 (24) [M–C8H10]+, 104 (100) [C8H8]+. – HRMS (C22H21N) calc. 299.1669; found

299.1670. – HRMS (APCI, C22H21N) calc. 300.1747 [M+H]+; found 300.1737 [M+H]+. Analytical data

matches that of the literature.[4]

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rac-[2]Paracyclo[2](1,4)carbazolophane (Carbazolophane)

In a 25 mL three neck flask equipped with a reflux condenser, 1.50 g of rac-4-N-

(phenyl)amino[2.2]paracyclophane (5.00 mmol, 1.00 equiv.), 225 mg of palladium acetate

(1.00 mmol, 20 mol%) and 306 mg of pivalic acid (3.00 mmol, 60 mol%) were dissolved

in 25 mL of acetic acid and the mixture was stirred at 120 °C for 7 h. While stirring, compressed air was added

continuously to the suspension using a Teflon hose. The crude product was dissolved in 100 mL of water and

50 mL of ethyl acetate. Then, the mixture was neutralized by adding solid potassium hydroxide and solid

sodium bicarbonate and extracted with 50 mL of ethyl acetate three times. The combined organic layers were

washed with 50 mL of brine and dried over Na2SO4. The dark brown filtrate was evaporated under reduced

pressure and the residue was purified by flash chromatography (silica, 10:1 cyclohexane:ethyl acetate) to yield

560 mg (38%, 1.88 mmol) of a white solid. – Rf = 0.29 (cyclohexane:ethyl acetate 10:1) – 1H NMR

(400 MHz, CDCl3) δ [ppm] = 8.06 (d, 3JHH = 7.9 Hz, 1H), 7.90 (br s, 1H), 7.46 (d, 3JHH = 8.2 Hz, 1H), 7.40

(t, 3JHH = 7.5 Hz, 1H), 7.29 – 7.23 (m, 1H), 6.63 (d, 3JHH = 7.5 Hz, 1H), 6.56 (d, 3JHH = 7.5 Hz, 1H), 6.50 (dd, 3JHH = 7.8 Hz, 4JHH = 1.9 Hz, 1H), 6.36 (dd, 3JHH = 7.8 Hz, 4JHH = 2.0 Hz, 1H), 5.94 (dd, 3JHH = 7.7 Hz, 4JHH

= 2.0 Hz, 1H), 5.22 (dd, 3JHH = 7.7 Hz, 4JHH = 1.9 Hz, 1H), 4.03 –3.98 (m, 1H), 3.42 – 3.27 (m, 1H), 3.18 –

2.87 (m, 6H). – 13C NMR (101 MHz, CDCl3) δ [ppm] = 140.14 (Cquat, CAr), 138.94 (Cquat, CAr), 138.01 (Cquat,

CAr), 137.41 (Cquat, CAr), 135.89 (Cquat, CAr), 132.12 (+, CArH), 131.60 (+, CArH), 131.09 (+, CArH), 126.57 (+,

CArH), 126.41 (+, CArH), 125.52 (Cquat, CAr), 125.35 (Cquat, CAr), 124.97 (+, CArH), 124.67 (+, CArH), 122.53

(+, CArH), 122.31 (Cquat, CAr), 119.78 (+, CArH), 110.76 (+, CArH), 34.05 (–, CH2), 33.86 (–, CH2), 33.35 (–,

CH2), 31.22 (–, CH2). – IR (ATR) ṽ [cm–1] = 3389 (w, v(NH)), 3031 (vw), 3005 (vw), 2986 (vw), 2923 (w),

2581 (vw), 1592 (vw), 1499 (w), 1455 (w), 1436 (w), 1393 (w), 1321 (w), 1298 (w), 1246 (w), 1026 (w), 931

(w), 871 (w), 805 (w), 770 (vw), 749 (m), 735 (m), 719 (w), 671 (w), 609 (w), 585 (w), 569 (vw), 514 (w),

470 (w) . – HRMS (APCI, C22H19N) calc. 298.1590 [M+H]+; found 298.1581 [M+H]+. Analytical data

matches that of the literature.[4]

S11

S12

2-(4-Fluorophenyl)-4,6-diphenyl-1,3,5-triazine

In a 250 mL Schlenk flask equipped with a reflux condenser 5.18 g of 2-

chlorophenyl-4,6-diphenyl-1,3,5-triazine (19.3 mmol, 1.00 equiv.), 4.06 g of (4-

fluorophenyl)boronic acid (29.0 mmol, 1.50 equiv.), 5.34 g of potassium carbonate

(38.7 mmol, 2.00 equiv.) and 1.50 g of Pd(PPh3)4 (1.30 mmol, 7 mol%) were

dissolved in 150 mL of dry toluene under argon atmosphere. 0.50 mL of water was

then added to the reaction mixture. The yellowish reaction mixture was stirred at 75 °C for 19 h. Then, the

mixture was diluted with 100 mL of water and 100 mL of ethyl acetate. After extraction, the organic layer was

washed with 100 mL of brine three times and dried over Na2SO4. The yellow filtrate was evaporated under

reduced pressure, and the brown crude product was purified by flash chromatography (silica, 2:1

cyclohexane:ethyl acetate) to yield 5.23 g (83%, 16.0 mmol) of a white fibrous solid. – Rf = 0.50 (CH/DCM

50:1). – 1H NMR (500 MHz, CDCl3) δ [ppm] = 8.83 – 8.71 (m, 6H), 7.66 – 7.54 (m, 6H), 7.25 (t, 3JHH =

8.6 Hz, 2H). – 13C NMR (125 MHz, CDCl3) δ [ppm] = 171.75, 170.76, 165.93 (Cquat, d, 1JCF = 253.0 Hz),

136.23 (Cquat, CAr), 132.73 (+, CAr), 132.52 (Cquat, d, 4JCF = 2.9 Hz, CAr), 131.43 (+, d, 3JCF = 9.0 Hz, CArH),

129.08 (+, CAr), 128.79 (+, CAr), 115.84 (+, d, 2JCF = 21.8 Hz, CArH). – 19F NMR (470 MHz, CDCl3) δ [ppm]

= –107.1 (1F). – IR (ATR) ṽ [cm–1] = 3055 (w), 1915 (w), 1601 (m), 1509 (s), 1446 (m), 1412 (m), 1362 (s),

1224 (m), 1175 (m), 1142 (m), 1066 (m), 1026 (m), 855 (m), 832 (m), 764 (s), 728 (m), 685 (s), 644 (m), 583

(m), 503 (m), 469 (w), 392 (w).– EA (C21H14FN3) calc. N: 12.84, C:77.05, H: 4.31; found N: 12.80, C: 76.95,

H: 4.31. – HRMS (APCI, C21H14FN3) calc. 328.1245 [M+H]+; found 328.1234 [M+H]+. Analytical data

matches that of the literature.[6]

S13

S14

9-(4-(4,6-Diphenyl-1,3,5-triazin-2-yl)phenyl)-9N-carbazole

In a pressure vial, 92.0 mg of carbazole (550 µmol, 1.00 equiv.), 360 mg of the

fluoride 2-(4-fluorophenyl)-4,6-diphenyl-1,3,5-triazine (1.10 mmol, 2.00 equiv.)

and 257 mg of tripotassium phosphate (1.21 mmol, 2.20 equiv.) were dissolved in

8 mL of DMSO and stirred at 115 °C for 16 h. After cooling to room temperature,

the mixture was diluted with 30 mL ethyl acetate and washed with 50 mL of brine three times. The organic

layer was dried over Na2SO4. Afterwards, the solvent was evaporated under reduced pressure and the residue

was purified by flash chromatography (silica, 50:1, 10:1, 5:1, 2:1 gradient cyclohexane:DCM) to yield

52.1 mg (42%, 110 µmol) of a yellow solid that luminesced. – Rf = 0.28 (cyclohexane/DCM 10:1). – Mp =

270 °C. – 1H NMR (500 MHz, CDCl3) δ [ppm] = 9.03 (d, 3JHH = 8.6 Hz, 2H), 8.83 (d, 3JHH = 8.2 Hz, 4H),

8.18 (d, 3JHH = 7.8 Hz, 2H), 7.83 (d, 3JHH = 8.5 Hz, 2H), 7.69 – 7.59 (m, 6H), 7.57 (d, 3JHH = 8.2 Hz, 2H), 7.46

(t, 3JHH = 7.7 Hz, 2H), 7.34 (t, 3JHH = 7.5 Hz, 2H). – 13C NMR (126 MHz, CDCl3) δ [ppm] = 171.95(Cquat,

CAr), 171.08 (Cquat, CAr), 141.75 (Cquat, CAr), 140.57 (Cquat, CAr), 136.27 (Cquat, CAr), 135.09 (Cquat, CAr),

132.82(+, CArH), 130.79 (+, CArH), 129.16 (+, CArH), 128.87(+, CArH), 126.88 (+, CArH), 126.30 (+, CArH),

123.89 (Cquat, CAr), 120.58 (+, CArH), 120.55(+, CArH), 110.07(+, CArH). – IR (ATR) ṽ [cm–1] = 3054 (vw),

2850 (vw), 2921 (w), 1589 (w), 1512 (m), 1444 (m), 1366 (m), 1223 (w), 1169 (w), 1026 (w), 827 (w), 765

(m), 737 (m), 720 (m), 686 (m), 647 (w), 621 (w), 562 (w), 505 (w), 466 (w), 418 (w). – EA (C33H22N4) calc.

C: 83.52, H: 4.67, N: 11.81; found C: 82.29, H: 4.56, N: 11.54. – HRMS (APCI, C33H22N4) calc. 475.1917

[M+H]+; found 475.1900 [M+H]+. Analytical data matches that of the literature.[7]

S15

S16

rac-1-(N-Carbazolophanyl)-4-(4,6-diphenyl-1,3,5-triazin-2-yl)-benzene

In a pressure vial, 125 mg of rac-[2]paracyclo[2](1,4)carbazolophane (420 µmol,

1.00 equiv.), 275 mg of 2-(4-fluorophenyl)-4,6-diphenyl-1,3,5-triazine (840 µmol,

2.00 equiv.) and 196 mg of tripotassium phosphate (924 µmol, 2.20 equiv.) were

dissolved in 8 mL of DMSO and stirred at 115 °C for 16 h. After cooling to room

temperature, the mixture was diluted with 30 mL of ethyl acetate and washed with

50 mL of brine three times. The organic layer was dried over Na2SO4. Afterwards, the solvent was evaporated

under reduced pressure and the residue was purified by flash chromatography (silica, 100:1, 50:1, 10:1, 5:1,

1:1 gradient cyclohexane:DCM) to yield 215 mg (84%, 355 µmol) of a yellow and highly luminescent solid.

– Rf = 0.28 (CH/DCM 10:1). – Mp = 263 °C. – 1H NMR (500 MHz, CDCl3) δ [ppm] = 9.03 (bs, 2H), 8.88 –

8.81 (m, 4H), 8.17 (d, 3JHH = 7.8 Hz, 1H), 7.72 – 7.57 (m, 8H), 7.56 (d, 3JHH = 8.1 Hz, 1H), 7.42 (t, 3JHH = 7.6

Hz, 1H), 7.36 (t, 3JHH = 7.4 Hz, 1H), 6.73 – 6.64 (m, 2H), 6.51 (dd, 3JHH = 7.8, 4JHH = 1.8 Hz, 1H), 6.35 (dd, 3JHH = 7.8, 4JHH = 1.8 Hz, 1H), 5.98 (dd, 3JHH = 7.6, 4JHH = 1.8 Hz, 1H), 5.54 (dd, 3JHH = 7.7, 4JHH = 1.8 Hz,

1H), 4.11 – 4.05 (m, 1H), 3.26 – 3.03 (m, 3H), 2.94 – 2.85 (m, 1H), 2.84 – 2.66 (m, 2H), 2.29 (ddd, 3JHH =

13.1, 9.6, 2JHH = 7.3 Hz, 1H). – 13C NMR (125 MHz, CDCl3) δ [ppm] = 171.95 (Cquat, CAr), 171.04 (Cquat,

CAr), 142.88 (Cquat, CAr), 140.68 (Cquat, CAr), 140.56 (Cquat, CAr), 138.11 (Cquat, CAr), 137.56 (Cquat, CAr), 136.26

(Cquat, CAr), 135.94 (Cquat, CAr), 134.94 (Cquat, CAr), 133.67 (+, CArH), 132.83 (+, CArH), 131.76 (+, CArH),

131.37 (+, CArH), 130.31 (+, CArH), 129.16 (+, CArH), 129.09 (+, CArH), 128.87 (+, CArH), 128.80 (+, CArH),

127.82 (+, CArH), 127.13 (Cquat, CAr), 126.71 (+, CArH), 125.88 (Cquat, CAr), 125.78 (+, CArH), 125.35 (+,

CArH), 124.59 (Cquat, CAr), 122.69 (+, CArH), 121.03 (+, CArH), 109.91 (+, CArH), 35.14 (–, CH2), 33.96 (–,

CH2), 33.57 (–, CH2), 33.26 (–, CH2). – IR (ATR) ṽ [cm–1] = 3030 (vw), 2927 (vw), 2852 (vw), 1587 (vw),

1510 (w), 1444 (w), 1395 (w), 1364 (w), 1173 (w), 1025 (w), 890 (vw), 831 (w), 765 (w), 739 (w), 686 (w),

639 (w), 597 (vw), 527 (vw), 511 (w), 482 (vw), 415 (vw). – EA (C43H32N4) calc. C: 85.40, H: 5.33, N: 9.26;

found C: 84.75, H: 5.24, N: 9.34. – HRMS (APCI, C43H32N4) calc. 605.2700 [M+H]+; found 605.2678

[M+H]+.

S17

S18

5. Chiral Separation and Determination of Alsolute Configuration An overview of the strategy is shown in Scheme S2.

Scheme S2. Synthetic approach to the chiral emitters and the determination of absolute configuration.

Since the final emitter CzpPhTrz is very unpolar, it was unsuitable for a racemate separation on a

semipreparative scale, but the free carbazolophane (Czp) was fit. The analytical HPLC chromatogram is

shown in Figure S4 to determine the enantiomeric excess, but it was also possible to separate the enantiomers

on a semipreparative scale using the identical stationary phase.

Figure S4. Analytical HPLC separation of Czp. A chiral Amylose-SA column from YMC was used as stationary phase with 10% isopropanol in n-hexane as the eluent with a 1.0 mL/min flow rate and detection at 256 nm.

To determine the absolute configuration (result already shown in Figure S4), the literature known bromide

PCP-Br was separated into its enantiomers via semipreparative chiral HPLC using chiralpak-AZ (20 ×

S19

250 mm, 5 µm) as the stationary phase and acetonitrile as the eluent (25 mL/min, 25 °C, 100 mg racemate

loading per run). The absolute configurations for the first eluent (tR 7.2 min) and second eluent (tR 8.4 min)

were determined by comparison of the circular dichroism (CD) spectra (Figure S5) with literature-known

experimental and calculated data,[9] as well as with theory.[10]

Figure S5. CD measurements in acetonitrile of 4-bromo[2.2]paracyclophane.

The final conversion to the respective enantioenriched emitter was then conducted with subsequent fractional

recrystallization in order to increase the enantiomeric excess (Figure S6). Comparing the enantiomeric excess

of (RP)-emitter (93%ee) with the (RP)-carbazolophane precursor (92%ee), the recrystallization did not serve

to increase the ee in a significant manner. As the final emitter does not present pH-active groups, analytical

HPLC runs had to be performed with a significantly reduced flow rate of 0.2 mL/min in order to observe a

separation of the enantiomers.

Figure S6. Analytical HPLC of CzpPhTrz emitters. Amylose-SA was used as the stationary phase with 2% isopropanol in n-hexane as the eluent with a 0.2 mL/min flow rate and detection at 256 nm. Top: Racemate for comparison. Middle: (SP) with a determined enantiomeric excess of 99%. Bottom: (RP) with a determined enantiomeric excess of 93%.

S20

6. Crystallography Single crystal X-ray diffraction data were collected on a STOE STADI VARI diffractometer with

monochromated Cu Ka (1.54186 Å) or Ga Ka (1.34143 Å) radiation at low temperature. Using Olex2,[11] the

structures were solved with the ShelXS[12] structure solution program using Direct Methods and refined with

the ShelXL[13] refinement package using Least Squares minimization. Refinement was performed with

anisotropic temperature factors for all non-hydrogen atoms; hydrogen atoms were calculated on idealized

positions. Crystallographic data for compounds CzPhTrz (CCDC 1871934) and CzpPhTrz (CCDC 1871935)

have been deposited with the Cambridge Crystallographic Data Centre.

Table S1. Crystal data and structure refinement information for CzPhTrz and CzpPhTrz.

Compound CzPhTrz CzpPhTrz

Empirical formula C33H22N4 C43H32N4 Formula weight 474.54 604.72 Temperature/K 160.2 180.2 Crystal system triclinic monoclinic Space group P1̄ P21/c a/Å 3.8653(2) 15.6193(6) b/Å 15.5368(8) 13.7087(4) c/Å 19.5050(12) 14.6312(5) α/° 101.550(4) 90 β/° 91.474(5) 94.394(3) γ/° 94.709(4) 90 Volume/Å3 1142.70(11) 3123.63(19) Z 2 4 ρcalc/g cm–3 1.379 1.286 µ/mm–1 0.413 0.586 F(000) 496.0 1272.0 Crystal size/mm3 0.22 × 0.04 × 0.03 0.34 × 0.28 × 0.02 Radiation GaKα (λ = 1.34143) CuKα (λ = 1.54186) 2Θ range for data collection/° 5.07 to 113.9 12.13 to 128.0 Index ranges –1 ≤ h ≤ 4, –19 ≤ k ≤ 19, –24 ≤ l ≤ 24 –17 ≤ h ≤ 18, –15 ≤ k ≤ 13, –17 ≤ l ≤ 14 Reflections collected 13397 14283 Independent reflections 4564 [Rint = 0.0509, Rσ = 0.0386] 5057 [Rint = 0.0604, Rσ = 0.0492] Indep. refl. with I ≥ 2σ(I) 3112 3700 Data/restraints/parameters 4564/0/334 5057/0/425 Goodness-of-fit on F2 0.922 1.035 Final R indexes [I ≥ 2σ(I)] R1 = 0.0470, wR2 = 0.1193 R1 = 0.0547, wR2 = 0.1415 Final R indexes [all data] R1 = 0.0682, wR2 = 0.1287 R1 = 0.0872, wR2 = 0.1569 Largest diff. peak/hole / e Å–3 0.19/–0.29 0.22/–0.22 CCDC number 1871934 1871935

S21

7. Electrochemical Characterization. Electrochemistry measurements. Cyclic Voltammetry (CV) analysis was performed on an Electrochemical

Analyzer potentiostat model 600D from CH Instruments. Samples were prepared as DCM solutions, which

were degassed by sparging with DCM-saturated nitrogen gas for 10 minutes prior to measurements. All

measurements were performed in 0.1 M DCM solution of tetrabutylammonium hexafluorophosphate, which

was used as the supporting electrolyte. An Ag/Ag+ electrode was used as the reference electrode while a glassy

carbon electrode and a platinum wire were used as the working electrode and counter electrode, respectively.

The redox potentials are reported relative to a saturated calomel electrode (SCE) with a ferrocene/ferrocenium

(Fc/Fc+) redox couple as the internal standard (0.46 V vs SCE).[14]

Figure S7. Cyclic Voltammograms and Differential Pulse Voltammograms of CzPhTrz and CzpPhTrz in degassed DCM (scan rate 100 mV s-1).

8. Thermal Analysis.

Figure S8. a.) TGA and b.) DSC measurements of CzPhTrz and CzpPhTrz.

S22

9. Photophysical Characterization. Photophysical measurements. Optically dilute solutions of concentrations on the order of 10-5 or 10-6 M were

prepared in HPLC grade solvent for absorption and emission analysis. Absorption spectra were recorded at

room temperature on a Shimadzu UV-1800 double beam spectrophotometer. Aerated solutions were bubbled

with compressed air for 5 minutes whereas degassed solutions were prepared via three freeze-pump-thaw

cycles prior to emission analysis using an in-house adapted fluorescence cuvette, itself purchased from Starna.

Steady-state emission and time-resolved emission spectra were recorded at 298 K using an Edinburgh

Instruments FLS980 fluorimeter. Samples were excited at 360 nm for steady-state measurements and at 378

nm for time-resolved measurements. Photoluminescence quantum yields for solutions were determined using

the optically dilute method[15] in which four sample solutions with absorbance of ca. 0.100, 0.080, 0.060 and

0.040 at 360 nm were used. Their emission intensities were compared with those of a reference, quinine sulfate,

whose quantum yield (Φr) in 1 N H2SO4 was determined to be 54.6% using absolute method.[16] The quantum

yield of the sample, ΦPL, can be determined by the equation ΦPL = Φr(Ar/As)((Is/Ir)(ns/nr)2, where A stands for

the absorbance at the excitation wavelength (λexc = 360 nm), I is the integrated area under the corrected

emission curve and n is the refractive index of the solvent with the subscripts “s” and “r” representing sample

and reference respectively. An integrating sphere was employed for quantum yield measurements for thin film

samples.[17] Doped thin films were prepared by mixing the sample (10 wt.%) and PMMA in CHCl3 followed

by spin-casting on a quartz substrate. The ΦPL of the films were then measured in air and by purging the

integrating sphere with N2 gas flow. Time-resolved PL measurements of the thin films were carried out using

the time-correlated single-photon counting technique. The samples were excited at 378 nm by a pulsed laser

diode (Picoquant, model PLS 370) and were kept in a vacuum of < 10−4 mbar. The singlet-triplet splitting

energy ∆EST was estimated by recording the prompt fluorescence spectra and phosphorescence emission at 77

K in 10 wt.% doped films in DPEPO. The films were excited by a Q-switched Nd:YAG laser emitting at 355

nm (Laser-export). Emission from the samples was focused onto a spectrograph (Chromex imaging, 250is

spectrograph) and detected on a sensitive gated iCCD camera (Stanford Computer Optics, 4Picos) having

subnanosecond resolution.

S23

Figure S9. Transient PL decay curves of a.) CzPhTrz and b.) CzpPhTrz in degassed PhMe (λexc = 378 nm).

Figure S10. Time-resolved PL decay curve of CzPhTrz in 10 wt.% doped film in DPEPO (λexc = 378 nm).

Figure S11. Prompt and delayed spectra (at 77K) of CzPhTrz in 10 wt.% doped film in DPEPO (λexc = 355 nm).

S24

Table S2. Absolute ΦPL measurements of doped films of CzPhTrz and CzpPhTrz in different host materials as a function of doping concentrations.

Host Material a

ΦbPL

/ %

CzPhTrz CzpPhTrz

Neat Film 20 28

10 wt. % PMMAc 25 45

1 wt.% DPEPO 39 43

10 wt.% DPEPOd 50 69

7 wt.% PPT - 62

15 wt.% mCP 48 65

10 wt.% CzSi - 60 a Thin films were prepared by vacuum deposition and values were determined using

an integrating sphere (λexc = 360 nm); degassing was done by N2 purge. b Within error

limit of +/- 2%. c Prepared by spin coating. d Average FPL value of 5 different

measurements.

S25

10. DFT modelling Computational methodology

DFT calculations were performed with the Gaussian 09 revision D.018 suite.[18] Initially the geometries of

both emitters in the ground state in the gas phase were optimized employing the PBE0[19] functional with the

standard Pople 6-31G(d,p) basis set.[20] Time-dependent DFT calculations were performed using the Tamm–

Dancoff approximation (TDA).[21] The molecular orbitals were visualized using GaussView 5.0 software.

Table S3. Optimized atomic coordinates of compound CzPhTrz obtained from DFT calculations.

--------------------------------------------------------------------- Center Atomic Atomic Coordinates (Å) Number Number Type X Y Z --------------------------------------------------------------------- 1 6 0 4.773569 -0.862680 0.732460 2 6 0 4.417040 -1.859427 1.638712 3 6 0 5.443086 -2.560657 2.259459 4 6 0 6.789580 -2.276506 1.994829 5 6 0 7.137384 -1.269447 1.105655 6 6 0 6.126249 -0.549447 0.468404 7 7 0 3.960676 -0.000119 -0.000095 8 6 0 4.773562 0.862550 -0.732544 9 6 0 6.126245 0.549440 -0.468354 10 6 0 4.417027 1.859274 -1.638811 11 6 0 7.137365 1.269565 -1.105483 12 6 0 5.443057 2.560636 -2.259431 13 6 0 6.789552 2.276616 -1.994662 14 1 0 8.180780 1.039180 -0.910700 15 1 0 5.192142 3.343626 -2.968680 16 1 0 7.565469 2.846334 -2.496194 17 6 0 2.555308 -0.000088 -0.000086 18 6 0 1.854024 -1.191682 -0.207762 19 6 0 1.854068 1.191534 0.207597 20 6 0 0.468611 -1.189587 -0.200125 21 1 0 2.405369 -2.107537 -0.392984 22 6 0 0.468659 1.189481 0.199997 23 1 0 2.405451 2.107375 0.392776 24 6 0 -0.239179 -0.000043 -0.000051 25 1 0 3.377652 2.074875 -1.861085 26 1 0 -0.088368 2.104991 0.364567 27 1 0 -0.088452 -2.105078 -0.364679 28 6 0 -1.713079 -0.000020 -0.000020 29 7 0 -2.334880 -1.163922 -0.210307 30 7 0 -2.334832 1.163906 0.210281 31 6 0 -3.670599 -1.112798 -0.203956 32 6 0 -3.670552 1.112827 0.203990 33 7 0 -4.381960 0.000027 0.000030 34 6 0 -4.408944 -2.368761 -0.437997 35 6 0 -5.807467 -2.375046 -0.427491 36 6 0 -3.715105 -3.560110 -0.673076 37 6 0 -6.500725 -3.557395 -0.649105

S26

38 1 0 -6.330264 -1.443074 -0.243633 39 6 0 -4.411881 -4.740332 -0.894910 40 1 0 -2.631060 -3.538579 -0.678537 41 6 0 -5.805106 -4.741625 -0.883339 42 1 0 -7.586509 -3.557121 -0.639614 43 1 0 -3.868595 -5.662526 -1.077752 44 1 0 -6.348818 -5.665719 -1.057032 45 6 0 -4.408845 2.368820 0.438033 46 6 0 -5.807369 2.375137 0.427659 47 6 0 -3.714955 3.560165 0.672984 48 6 0 -6.500578 3.557513 0.649283 49 1 0 -6.330205 1.443170 0.243896 50 6 0 -4.411683 4.740415 0.894822 51 1 0 -2.630911 3.538609 0.678342 52 6 0 -5.804909 4.741739 0.883388 53 1 0 -7.586363 3.557263 0.639899 54 1 0 -3.868358 5.662607 1.077561 55 1 0 -6.348583 5.665855 1.057087 56 1 0 3.377673 -2.075154 1.860873 57 1 0 5.192175 -3.343655 2.968696 58 1 0 7.565503 -2.846112 2.496471 59 1 0 8.180791 -1.038962 0.910969 ---------------------------------------------------------------------

S27

Table S4. Optimized atomic coordinates of compound CzpPhTrz obtained from DFT calculations.

--------------------------------------------------------------------- Center Atomic Atomic Coordinates (Å) Number Number Type X Y Z --------------------------------------------------------------------- 1 6 0 3.440431 0.948624 0.275039 2 6 0 3.243274 1.822784 -0.806331 3 6 0 4.303074 2.698901 -1.039168 4 6 0 5.566582 2.518690 -0.468422 5 6 0 5.835094 1.434080 0.361440 6 6 0 4.719719 0.733967 0.845536 7 1 0 4.193762 3.436990 -1.830313 8 1 0 6.392686 3.126364 -0.828918 9 6 0 7.232130 0.872726 0.442006 10 1 0 7.553635 0.696496 1.474149 11 1 0 7.918424 1.620972 0.033435 12 6 0 2.199959 1.623781 -1.880737 13 6 0 7.403438 -0.473780 -0.374554 14 1 0 7.420793 -1.316893 0.322658 15 1 0 8.384298 -0.443938 -0.862018 16 6 0 2.358535 0.253398 -2.649211 17 1 0 1.634993 -0.464003 -2.248875 18 1 0 2.084884 0.428951 -3.695888 19 6 0 6.289233 -0.686461 -1.367634 20 6 0 6.111095 0.194410 -2.438341 21 6 0 4.856110 0.375390 -3.004807 22 1 0 6.926192 0.851480 -2.732659 23 6 0 3.991242 -1.391904 -1.655618 24 6 0 3.746315 -0.318458 -2.514099 25 1 0 4.711584 1.170602 -3.732519 26 1 0 3.160048 -2.003509 -1.313607 27 1 0 2.321985 2.441471 -2.598200 28 1 0 1.172271 1.686045 -1.510737 29 6 0 5.249362 -1.575920 -1.088996 30 7 0 2.560484 -0.007471 0.784653 31 6 0 3.248806 -0.821895 1.680999 32 6 0 4.595927 -0.398973 1.733471 33 6 0 2.770824 -1.863327 2.473613 34 6 0 5.485340 -1.071529 2.576599 35 6 0 3.678835 -2.516536 3.296520 36 6 0 5.024778 -2.131803 3.344186 37 1 0 6.523731 -0.765106 2.640309 38 1 0 3.333955 -3.338229 3.916839 39 1 0 5.711323 -2.662458 3.996380 40 1 0 5.376949 -2.322185 -0.309325 41 6 0 1.162725 -0.005576 0.636727 42 6 0 0.439343 1.177575 0.814729 43 6 0 0.489733 -1.189719 0.320700 44 6 0 -0.938266 1.174084 0.672754 45 1 0 0.972736 2.088822 1.065644

S28

46 6 0 -0.890572 -1.190200 0.193654 47 1 0 1.060113 -2.098479 0.159525 48 6 0 -1.619027 -0.009261 0.365494 49 1 0 1.726000 -2.152483 2.455883 50 1 0 -1.424794 -2.100042 -0.055946 51 1 0 -1.512184 2.083609 0.810054 52 6 0 -3.085726 -0.009688 0.222618 53 7 0 -3.723869 1.155569 0.364986 54 7 0 -3.685104 -1.174756 -0.040237 55 6 0 -5.052375 1.105713 0.225890 56 6 0 -5.015218 -1.123104 -0.162987 57 7 0 -5.741607 -0.008090 -0.039397 58 6 0 -5.807776 2.364424 0.374905 59 6 0 -7.199479 2.370572 0.236412 60 6 0 -5.136717 3.558933 0.655770 61 6 0 -7.908422 3.556059 0.376767 62 1 0 -7.704633 1.436009 0.019372 63 6 0 -5.849179 4.742287 0.795890 64 1 0 -4.057683 3.537622 0.760074 65 6 0 -7.235473 4.743497 0.656648 66 1 0 -8.988813 3.555739 0.268229 67 1 0 -5.323586 5.667008 1.014199 68 1 0 -7.791549 5.670028 0.766472 69 6 0 -5.729643 -2.381287 -0.452564 70 6 0 -7.119832 -2.381231 -0.605373 71 6 0 -5.021948 -3.581341 -0.574996 72 6 0 -7.791177 -3.565651 -0.877553 73 1 0 -7.653745 -1.442650 -0.506961 74 6 0 -5.696903 -4.763908 -0.846453 75 1 0 -3.944655 -3.565033 -0.453118 76 6 0 -7.081865 -4.758688 -0.998453 77 1 0 -8.870543 -3.560148 -0.995693 78 1 0 -5.142950 -5.693111 -0.940018 79 1 0 -7.608390 -5.684633 -1.210880 ---------------------------------------------------------------------

S29

11. Device Characterization. OLED fabrication and characterization. The OLED devices were fabricated in bottom emitting architecture

via vacuum sublimation in high vacuum at a base pressure of 2-5·10-7 mbar. The organic layer sequence and

the metal cathode were deposited onto pre-cleaned glass substrates coated with indium tin oxide (ITO) which

has a sheet resistance of around 30 Ω/sq. A pre-patterned ITO glass substrate was treated by ultrasonic

cleaning in acetone and isopropanol consecutively and then treated by oxygen plasma before the transfer to

the vacuum chamber. Organic layers were deposited at a rate of 0.3-0.6 Å/s, which was controlled in situ using

the quartz crystal monitors. Doping of the emission layers was achieved through co-evaporation of the emitter

and host materials. The electron injection layer LiF was deposited at a rate of 0.10 Å/s while the Al cathode

was deposited at a rate of 0.5 Å/s through the shadow mask defining the top electrode. The spatial overlap of

the anode and cathode electrodes determined the active area of the OLED which was estimated to be 2 mm2.

All the devices were encapsulated with glass lids and UV epoxy resin inside the inert atmosphere. The

luminance-current-voltage characteristics were measured in an ambient environment using a Keithley 2400

source meter and Keithley 2000 multimeter connected to a calibrated Si photodiode. The external quantum

efficiency was calculated assuming Lambertian emission distribution. The electroluminescence spectra were

recorded by an Andor DV420-BV CCD spectrometer.

S30

12. References [1] F. Vögtle, P. Neumann, Tetrahedron Lett. 1969, 60, 5329–5334. [2] R. S. Cahn, C. Ingold, V. Prelog, Angew. Chem. Int. Ed. 1966, 5, 385–415. [3] P. Lennartz, G. Raabe, C. Bolm, Isr. J. Chem. 2012, 52, 171–179. [4] P. Lennartz, G. Raabe, C. Bolm, Isr. J. Chem. 2012, 52, 171-179. [5] C. Braun, S. Bräse, L. L. Schafer, European Journal of Organic Chemistry 2017, 2017, 1760-1764. [6] W. Guo, Org Biomol Chem 2015, 13, 10285-10289. [7] J. Xiao, X. K. Liu, X. X. Wang, C. J. Zheng, F. Li, Organic Electronics 2014, 15, 2763-2768. [8] C. Braun, Ph.D. thesis, Karlsruhe Institute of Technology 2017. [9] M. Toda, Y. Inoue, T. Mori, ACS Omega 2018, 3, 22–29. [10] C. Rosini, R. Ruzziconi, S. Superchi, F. Fringuelli, O. Piermatti, Tetrahedron: Asymmetry 1998, 9,

55–62. [11] O. V. Dolomanov, L. J. Bourhis, R. J. Gildea, J. A. K. Howard, H. Puschmann, J. Appl. Crystallogr.

2009, 42, 339-341. [12] G. Sheldrick, Acta Crystallogr., Sect. A 2008, 64, 112-122. [13] G. Sheldrick, Acta Crystallogr., Sect. C: Cryst. Struct. Commun. 2015, 71, 3-8. [14] N. G. Connelly, W. E. Geiger, Chem. Rev. 1996, 96, 877-910. [15] G. A. Crosby, J. N. Demas, J. Phys. Chem. 1971, 75, 991-1024. [16] W. H. Melhuish, J. Phys. Chem. 1961, 65, 229-235. [17] N. C. Greenham, I. D. W. Samuel, G. R. Hayes, R. T. Phillips, Y. A. R. R. Kessener, S. C. Moratti,

A. B. Holmes, R. H. Friend, Chem. Phys. Lett. 1995, 241, 89-96. [18] M. J. Frisch, G. W. Trucks, H. B. Schlegel, G. E. Scuseria, M. A. Robb, J. R. Cheeseman, G.

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[19] C. Adamo, V. Barone, J. Chem. Phys. 1999, 110, 6158-6170. [20] J. A. Pople, J. S. Binkley, R. Seeger, Int. J. Quant. Chem. Symp. 1976, 10, 1. [21] M. Moral, L. Muccioli, W. J. Son, Y. Olivier, J. C. Sancho-García, J. Chem. Theory Comput. 2015,

11, 168-177.